CN106588628B - The preparation method of carboxylic acid - Google Patents
The preparation method of carboxylic acid Download PDFInfo
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- CN106588628B CN106588628B CN201611139651.4A CN201611139651A CN106588628B CN 106588628 B CN106588628 B CN 106588628B CN 201611139651 A CN201611139651 A CN 201611139651A CN 106588628 B CN106588628 B CN 106588628B
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- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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Abstract
The present invention provides a kind of preparation methods of carboxylic acid, comprising: the polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic acid；The composite catalyst includes hydrogenation catalyst and lewis acid；Wherein, a, b it is independent be selected from 1~10 integer；M, n it is independent be selected from 1~30000 integer；R1、R2Independent one or more of the alkyl selected from H and C1~C12.For polyhydroxyalkanoate shown in formula (I) of the present invention under conditions of hydrogenation catalyst and lewis acid composite catalyst, hydrogenolysis depolymerization obtains carboxylic acid compound.Reaction condition provided by the invention is mild, high income, and by-product is few with traditional method compared with, meets the requirement of Green Chemistry, with more industrial value.
Description
Technical field
The present invention relates to compound synthesis technical fields, more particularly, to a kind of preparation method of carboxylic acid.
Background technique
Polyhydroxyalkanoate (PHA) is a kind of Biodegradable high-molecular compound synthesized in bacterial cell, very
It is multi-field to have a wide range of applications.Current main research direction concentrates in the development and application of PHA.As one kind by
The Biopolvester intracellular of Microbe synthesis, PHA are the deposits of energy and carbon source of the multiple-microorganism in energy and carbon source surplus
Substance.The prior art is mostly using PHA as the deposit substance of energy, by reacting PHA with excessive methanol, through transesterification solution
Poly-, obtained hydroxy fatty acid methyl esters can be directly as bio-fuel.
Carboxylic acid is a kind of important compound, is the final product of many oxidation operations.It is generally existing in nature,
It has a wide range of applications in industry, agricultural and field of medicaments.
The method of prior art preparation carboxylic acid mainly has oxidizing process, carbonylation method, Hydrolyze method and CO2Prize law etc.；Specifically
Say, oxidizing process be the oxidation of hydrocarbon, the oxidation of primary alconol or aldehyde compound, the oxidation of methyl ketone；Carbonylation method is alcohols chemical combination
The hydrated carbonyl of the carbonylation of object, alkene；Hydrolyze method is cyanides hydrolysis, lipoid substance hydrolysis, amides chemical combination
Object hydrolysis；CO2Prize law is organometallic reagent and CO2Reaction, Kolbe-Schmitt reaction；Additionally pass through including methyl ketone
Haloform reaction prepares carboxylic acid.But the above method prepares carboxylic acid reaction condition harshness, and by-product is more, and yield is low.
Summary of the invention
In view of this, the present invention provides the technical problem to be solved in the present invention is that providing a kind of preparation method of carboxylic acid
Carboxylic acid preparation method by-product it is few, high income.
The present invention provides a kind of preparation methods of carboxylic acid, comprising:
The polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic
Acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；
Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.
Preferably, described a, b it is independent be selected from 1~8 integer；M, n it is independent be selected from 1~20000 integer；R1、R2Solely
Vertical one or more of the alkyl selected from H and C1~C8.
Preferably, the hydrogenation catalyst is noble metal carrier catalyst.
Preferably, the noble metal carrier catalyst carrier is active carbon, and metal is selected from one of palladium, platinum, rhodium, ruthenium
Or it is several.
Preferably, the lewis acid is metal trifluoroacetate mesylate.
Preferably, the lewis acid is selected from AgOTf, Cu (OTf)2、Al(OTf)3、Fe(OTf)3、Zr(OTf)4、Hf
(OTf)4、Nb(OTf)5、Ta(OTf)5With W (OTf)6One or more of.
Preferably, the mole of the hydrogenation catalyst is the 0.01%~5% of polyhydroxyalkanoate mole.
Preferably, the lewis acidic mole is the 0.5%~10% of polyhydroxyalkanoate mole.
Preferably, the pressure of the hydrogen is 1~100atm.
Preferably, the reaction temperature be 80 DEG C~250 DEG C, the reaction time be 0.5~for 24 hours.
Compared with prior art, the present invention provides a kind of preparation methods of carboxylic acid, comprising: the poly- hydroxyl as shown in formula (I)
Base aliphatic ester reacts in the presence of composite catalyst with hydrogen, obtains carboxylic acid；The composite catalyst includes adding hydrogen
Catalyst and lewis acid；Wherein, a, b it is independent be selected from 1~10 integer；M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.Polyhydroxyalkanoate shown in formula (I) of the present invention
Under conditions of hydrogenation catalyst and lewis acid composite catalyst, hydrogenolysis depolymerization obtains carboxylic acid compound.The present invention provides
Reaction condition is mild, high income, by-product is few with traditional method compared with, the requirement of composite green chemistry, has more industrial
Value.
Specific embodiment
The present invention provides a kind of preparation methods of carboxylic acid, comprising:
The polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic
Acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；
Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.
The present invention in the presence of composite catalyst, reacts polyhydroxyalkanoate with hydrogen, obtains carboxylic acid.It is excellent
Choosing is specially in the reactor to mix polyhydroxyalkanoate and composite catalyst, under the atmosphere of hydrogen, is stirred to react, obtains
To carboxylic acid.
For the present invention for the reactor without limiting, reactor well known to those skilled in the art is of the invention
For the stirring without limiting, stirring well known to those skilled in the art, preferably magnetic agitation.The stirring
Speed is preferably 400~600r/min；More preferably 500~600r/min.
Polyhydroxyalkanoate of the present invention is polyhydroxyalkanoate well known to those skilled in the art, is by very much
A kind of polyester intracellular of bacterium synthesis, exists primarily as the Stored Matter of carbon source and the energy in vivo, it has
There are biodegradability not available for physicochemical characteristic and synthetic plastic similar to synthetic plastic, biocompatibility, optics living
Property, piezoelectricity, gas phase are every many excellent in performance such as property.
Shown in polyhydroxyalkanoate of the present invention such as formula (I):
Wherein, a, b it is independent be selected from 1~10 integer；Preferably 1~8 integer；More preferably 1~6 integer.
M, n it is independent be selected from 1~30000 integer；It is preferably selected from 1~20000 integer；The polyhydroxyalkanoate
Number-average molecular weight be preferably 1.0 × 105~2.0 × 105。
R1、R2Independent one or more of the alkyl selected from H and C1~C12.It is preferably selected from the alkyl of H and C1~C8
One or more of；It is more preferably selected from one or more of the alkyl of H and C1~C6；The alkyl include straight chained alkyl and
Branched alkyl；The alkyl includes substituted or unsubstituted alkyl, and the present invention is to the substituent group for replacing alkyl without limit
It is fixed, it can be ester group well known to those skilled in the art, cyano, halogen.
In the present invention, described a, b；m,n；R1、R2It can be identical or different；That is, above-mentioned polyhydroxyalkanoate
It can be homopolymer or copolymer；
Polyhydroxyalkanoate of the present invention includes but is not limited to following particular compounds:
Homopolymer: poly- 3- hydracrylic acid, poly- 3-hydroxybutyrate, poly- 3- hydroxypentanoic acid, poly- 3- hydroxycaproic acid, poly- 3- hydroxyl heptan
Sour, poly- 3- Hydroxyoctanoic acid；
Copolymer: poly- hydracrylic acid hydroxypentanoic acid, polyhydroxybutyrate hydroxycaproic acid, polyhydroxybutyrate hydroxypentanoic acid, poly- hydroxyl
Base butyric acid hydroxypentanoic acid hydroxycaproic acid.
The polyhydroxyalkanoate that the present invention meets above-mentioned condition can carry out hydrogenolysis depolymerization reaction of the invention, obtain carboxylic
Acid.
The present invention for the polyhydroxyalkanoate source without limit, it is commercially available.
Composite catalyst of the present invention includes hydrogenation catalyst and lewis acid.
In the present invention, the hydrogenation catalyst is preferably noble metal carrier catalyst.The noble metal support type is urged
Agent carrier is preferably active carbon, and metal is preferably selected from one or more of palladium, platinum, rhodium, ruthenium；The noble metal support type is urged
Agent is more preferably Pd/C, Pt/C or Ru/C.
In the present invention, the lewis acid is preferably metal trifluoroacetate mesylate；More preferably AgOTf, Cu (OTf)2、
Al(OTf)3、Fe(OTf)3、Zr(OTf)4、Hf(OTf)4、Nb(OTf)5、Ta(OTf)5With W (OTf)6One or more of.
In the present invention, the mole of the hydrogenation catalyst be preferably polyhydroxyalkanoate mole 0.01%~
5%；More preferably 0.1%~3%；Most preferably 0.5%~2%；The lewis acidic mole is preferably poly- hydroxyl rouge
The 0.5%~10% of fat acid esters mole；More preferable 1%~8%；Most preferably 2%~6%.The hydrogenation catalyst and road
The mass ratio of Lewis acid is preferably (1~100): (1~100).
In the present invention, the atmosphere of the hydrogen be using the air in hydrogen metathesis reactor, preferably under normal pressure into
Row.Hydrogen balloon is more preferably connect above reactor.The pressure of the hydrogen is preferably 1~100atm；It is more preferably 1~50 big
Air pressure；Most preferably 1~20 atmospheric pressure；It is the most preferably 1~10 atmospheric pressure.
In the present invention, the reaction temperature is preferably 80 DEG C~250 DEG C, more preferably 100 DEG C~200 DEG C；Most preferably
It is 110 DEG C~180 DEG C；It is the most preferably 120 DEG C~150 DEG C；The reaction time is preferably 0.5~for 24 hours；More preferably 2~
20h；Most preferably 4~16h；It is the most preferably 8~14h.
The present invention is by the control of the parameters such as above-mentioned reaction temperature, reaction raw materials molar ratio, Hydrogen Vapor Pressure, so that final system
Standby obtained carboxylic acid high income.
In the present invention, according to the selection of reaction temperature and the selection of specific polyhydroxyalkanoate, solvent also has not
Same selection:
When reaction temperature is more than the fusing point of polyhydroxyalkanoate, it is not necessarily to reaction dissolvent；
When fusing point of the reaction temperature lower than polyhydroxyalkanoate is, it is preferable to use reaction dissolvent.
In the present invention, the solvent is preferably one or more of carboxylic acids, hydro carbons and ether solvent；Including but not
It is limited to for methylene chloride, acetic acid, acetic acid, propionic acid, dioxane, tetrahydrofuran or normal octane.
In the present invention, after completion of the reaction, preferably through isolated carboxylic acid sterling.
The separation is preferably with solvent dissolution, filtering, vacuum distillation, tool of the present invention for the filtering, vacuum distillation
Body mode is well known to those skilled in the art to filter, be evaporated under reduced pressure without limiting.The solvent includes but is not limited to be
Methylene chloride, acetic acid, acetic acid, propionic acid, dioxane, tetrahydrofuran or normal octane.
After the completion of the present invention separates carboxylic acid, it is preferably also included in the catalyst system of separation carboxylic acid and rejoins the poly- hydroxyl of raw material
Base aliphatic ester is passed through hydrogen, carries out catalytic hydrogenolytic cleavage again, can reuse to catalyst system.
The present invention provides a kind of preparation methods of carboxylic acid, comprising: the polyhydroxyalkanoate as shown in formula (I) is compound
It in the presence of catalyst, reacts with hydrogen, obtains carboxylic acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；R1、R2Independent one or more of the alkyl selected from H and C1~C12.This hair
Polyhydroxyalkanoate shown in bright formula (I) is under conditions of hydrogenation catalyst and lewis acid composite catalyst, hydrogenolysis depolymerization,
Obtain carboxylic acid compound.Reaction condition provided by the invention is mild, high income, and by-product is few with traditional method compared with, accords with
The requirement of Green Chemistry is closed, industrial value is had more.
Gas-chromatography is carried out to the carboxylic acid being prepared present invention preferably employs following manner and nuclear-magnetism is identified:
Gas chromatograph: GC-2014C, chromatographic column: DM-wax column (30m*0.32mm*0.25 μm)；Temperature program: 100 DEG C
(5min) → 10 DEG C/min → 180 DEG C (3min) → 20 DEG C/min → 240 DEG C (10min) injector temperature: 260 DEG C of detector temperature
Degree: 280 DEG C
Nuclear-magnetism: 400 spectrometer of model Bruker Avance is detected at room temperature.
In order to further illustrate the present invention, with reference to embodiments to the preparation side of carboxylic acid compound provided by the invention
Method is described in detail.
Examples 1 to 3
Raw material uses poly- hydroxymethylbutyrate ester (PHB), the i.e. homopolymer of 3-hydroxybutyrate, purity 99.9%, the degree of polymerization
It is 1500.To be put into after 10g raw material break process in the schlenk bottle of 100ml, be added the propionic acid of 15ml, 0.5% Pd/C and
2% W (OTf)6, apply the hydrogen pressure of 1atm, 100 DEG C~135 DEG C be heated in magnetic stirring apparatus, reaction keeps 8~12
Hour, revolving speed 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally use inspection of the present invention
Survey mode is measured.Specific experimental temperature, reaction time and testing result are listed in Table 1 below, and table 1 is the embodiment of the present invention 1
~15 reaction conditions and yield results.The nuclear magnetic data of product n-butyric acie is as follows:1H NMR(400MHz,CDCl3) δ=
2.34 (t, J=7.4,2H), 1.74-1.60 (m, 2H), 0.98 (t, J=7.4,3H)13C NMR(101MHz,CDCl3) δ=
180.59,35.97,18.12,13.53.
Embodiment 4~9
Raw material uses poly- hydroxymethylbutyrate ester (PHB), purity 99.9%, the degree of polymerization 1500.By the broken place of 10g raw material
It is put into miniature high pressure reaction still after reason, the W (OTf) of 0.5% Pd/C and 2% is added6, solvent using 15ml acetic acid, third
Acid, dioxane, tetrahydrofuran or normal octane apply the hydrogen pressure of 1,5 or 10atm, 135 are heated in magnetic stirring apparatus
DEG C, reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.It is final to use this
The invention detection mode is measured.Testing result is listed in Table 1 below, and table 1 is the reaction item of the embodiment of the present invention 1~15
Part and yield results.
Embodiment 10~15
Raw material uses poly- hydroxymethylbutyrate ester (PHB), purity 99.9%, the degree of polymerization 1500.By the broken place of 10g raw material
Be put into after reason in the schlenk bottle of 100ml, solvent use 15ml propionic acid, hydrogenation catalyst select 0.5% Pd/C or
0.5% Pt/C, fluoroform sulphonate select W (OTf)6、Hf(OTf)4、Al(OTf)3、Ta(OTf)5、Nb(OTf)5Or Zr
(OTf)4, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed 500r/
min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Inspection
The results are shown in Table 1 for survey, and table 1 is the reaction condition of the embodiment of the present invention 1~15 and yield results.
The reaction condition of 1 embodiment of the present invention of table 1~15 and yield results
Embodiment 16
Raw material is changed to polyhydroxybutyrate hydroxyl valerate (PHBV), the as copolymerization of 3-hydroxybutyrate and 3- hydroxypentanoic acid
Ester, wherein ratio shared by 3-hydroxybutyrate is that the ratio of 12%, 3- hydroxypentanoic acid is 88%, purity 99.9%, the degree of polymerization
It is 10000.It will be put into after 10g raw material break process in the schlenk bottle of 100ml, the propionic acid of 15ml, 0.5% Pd/C be added
With 2% W (OTf)6, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed
For 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally carried out using detection mode of the present invention
Measurement.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 17
Raw material is changed to polyhydroxybutyrate hydroxycaproate (PHBHHx), as 3-hydroxybutyrate and 3- hydroxycaproic acid is total to
Polyester, wherein ratio shared by 3-hydroxybutyrate is that the ratio of 14%, 3- hydroxycaproic acid is 86%, purity 99.9%, polymerization
Degree is 10000.It will be put into after 10g raw material break process in the schlenk bottle of 100ml, the propionic acid of 15ml, 2% Pd/C be added
With 4% W (OTf)6, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed
For 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally carried out using detection mode of the present invention
Measurement.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 18
Raw material is changed to another polyhydroxybutyrate hydroxycaproate (PHBHHx), wherein ratio shared by 3-hydroxybutyrate
Example is that the ratio of 29%, 3- hydroxycaproic acid is 71%, purity 99.9%, the degree of polymerization 15000.By 10g raw material break process
After be put into miniature high pressure reaction device, the W (OTf) of 0.5% Pd/C and 1% is added in solvent-free system6, apply the hydrogen of 5atm
Pressure is heated to 150 DEG C in magnetic stirring apparatus, and reaction is kept for 6 hours, revolving speed 500r/min.It is then cooled down, is filtered
Remove heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is
The reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 19
Raw material is changed to poly- Hydroxyoctanoic acid ester (PHO), the i.e. homopolymer of 3- Hydroxyoctanoic acid, purity 99.9%, the degree of polymerization
It is 3000.To be put into miniature high pressure reaction still after 10g raw material break process, solvent-free system, be added 0.5% Pd/C and
2% W (OTf)6, apply the hydrogen pressure of 10atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 6 hours, and revolving speed is
500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally surveyed using detection mode of the present invention
It is fixed.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.Product caprylic acid
Nuclear magnetic data it is as follows:1H NMR(400MHz,CDCl3) δ=2.35 (t, J=7.5,2H), 1.67-1.59 (m, 2H), 1.36-
1.25 (m, 8H), 0.88 (t, J=6.9,3H)13C NMR(101MHz,CDCl3) δ=180.48,34.11,31.64,29.02,
28.91,24.68,22.60,14.07.
Embodiment 20
Raw material is changed to poly- valerolactone (PVL), purity 99.9%, the degree of polymerization 6000.After 10g raw material break process
Be put into miniature high pressure reaction still, be added 15ml acetic acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen pressure of 1atm,
180 DEG C are heated in magnetic stirring apparatus, reaction is kept for 9 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove
Heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is this hair
Bright embodiment 16~22 reaction condition and yield results.The nuclear magnetic data of product valeric acid is as follows:1H NMR(400MHz,
CDCl3) δ=2.36 (t, J=7.5,2H), 1.68-1.57 (m, 2H), 1.43-1.32 (m, 2H), 0.93 (t, J=7.4,3H)
.13C NMR(101MHz,CDCl3) δ=180.75,33.86,26.71,22.17,13.68.
Embodiment 21
Raw material is changed to polycaprolactone (PCL), purity 99.9%, the degree of polymerization 8000.After 10g raw material break process
Be put into miniature high pressure reaction still, be added 15ml propionic acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen pressure of 1atm,
135 DEG C are heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove
Heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is this hair
Bright embodiment 16~22 reaction condition and yield results.The nuclear magnetic data of product n-caproic acid is as follows:1H [NMR(400MHz,
CDCl3) δ=2.35 (t, J=7.5,2H), 1.70-1.58 (m, 2H), 1.41-1.27 (m, 4H), 0.90 (t, J=6.9,3H)
.13C NMR(101MHz,CDCl3) δ=180.57,34.10,31.20,24.36,22.29,13.86.
Embodiment 22
Raw material is changed to poly- ε-decalactone (PDL), purity 99.9%, the degree of polymerization 5000.By 10g raw material break process
Be put into the schlenk bottle of 100ml afterwards, be added 15ml butyric acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen of 1atm
Pressure is heated to 135 DEG C in magnetic stirring apparatus, and reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, mistake
Filter out heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, table 2
For the reaction condition of the embodiment of the present invention 16~22 and yield results.The nuclear magnetic data of product n-capric acid is as follows:1H NMR
(400MHz,CDCl3) δ=2.35 (t, J=7.5,2H), 1.67-1.59 (m, 2H), 1.22-1.36 (m, 14H), 0.88 (t, J
=6.8,3H)13C NMR(101MHz,CDCl3) δ=180.59,34.14,31.90,29.56,29.45,29.32,29.25,
29.07,24.67,22.69,14.11.
The reaction condition of 2 embodiment of the present invention of table 16~22 and yield results
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of carboxylic acid, comprising:
The polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic acid；
The composite catalyst is hydrogenation catalyst and lewis acid；The hydrogenation catalyst is noble metal carrier catalyst；
The lewis acid is metal trifluoroacetate mesylate；
Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.
2. preparation method according to claim 1, which is characterized in that described a, b be independent be selected from 1~8 integer；m,n
It is independent be selected from 1~20000 integer；R1、R2Independent one or more of the alkyl selected from H and C1~C8.
3. preparation method according to claim 1, which is characterized in that the noble metal carrier catalyst carrier is activity
Charcoal, metal are selected from one or more of palladium, platinum, rhodium, ruthenium.
4. preparation method according to claim 1, which is characterized in that the lewis acid is selected from AgOTf, Cu (OTf)2、Al
(OTf)3、Fe(OTf)3、Zr(OTf)4、Hf(OTf)4、Nb(OTf)5、Ta(OTf)5With W (OTf)6One or more of.
5. preparation method according to claim 1, which is characterized in that the mole of the hydrogenation catalyst is poly- hydroxyl rouge
The 0.01%~5% of fat acid esters mole.
6. preparation method according to claim 1, which is characterized in that the lewis acidic mole is poly- hydroxy aliphatic
The 0.5%~10% of acid esters mole.
7. preparation method according to claim 1, which is characterized in that the pressure of the hydrogen is 1~100atm.
8. preparation method according to claim 1, which is characterized in that the reaction temperature is 80 DEG C~250 DEG C, when reaction
Between for 0.5~for 24 hours.
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| CN1449371A (en) * | 2000-08-24 | 2003-10-15 | 巴斯福股份公司 | Method for the catalytic decomposition of lactones |
| CN105873895A (en) * | 2013-12-31 | 2016-08-17 | Bp北美公司 | Method for forming an aromatic diacid and/or an aromatic diacid precursor from a polyester-containing feedstock |
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